Film forming compositions



United States Patent 2,987,409 FILM FORMING COMPOSITIONS Paule Valls, Paris, and Yves Etienne, Vincennes, France, assignors to Eastman Kodak Company, Rochester,

2,987,409 I Patented June 6, 1961 tensile strength of cellulose derivative films. A further object is to provide a coagulant which is compatible with solvents used for cellulose derivatives and which results in rapid coagulation of cellulose derivative coatings on N.Y., a corporation of New Jersey 5 a highly polisheq casting Surfiice No Drawing. Filed Apr. 29, 1959,5613 809,616 The above obyects are earned out by 1ncorporat1ng a 3 Claims 1. 105 17 compound selected from the class consisting of tnmethylcyclohexanone, and metadioxane having the following This invention concerns novel cellulose organic acid general formula: ester compositions having improved stability and adapted 10 for rapid coating on a polished rotating surface.

Cellulose derivative sheets or films are ordinarily pro- R, 0-0 R5 duced by depositing a cellulose derivative solution or dope in the form of a film on the highly polished surface of a slowly-rotating wheel or band, causing the film to set by evaporation of solvent, stripping the film and curing out Rs R1 any residual solvent. The compositions generally employed in the manufacture of films are of such nature In whlch the groups R1-Rs are hydrogen atoms or 9 that the fil attain a Solid or semi solid condition pep valent hydrocarbon groups such that the molecular welght mitting removal of the material from the film forming of the metadwXaPe 15 from 88 to The groups may surface only by gradual evaporation of solvent. the Same dlfierent- In order to increase the speed of coating cellulose mete-ilwliaese of the above formula can be derivatives onto rapidly moving casting wheels, coagulants Pal-ed ,accordmg to F methods Such as by the are added to the cellulose ester dope which cause the densatlon of a 9 and an aldehyde or a ketone material to gel or coagulate permitting the material to be 2 5 the Presence of an and": catalyst stripped from the film without the necessity of removing prderably the coagula-Pt constltutes from 5 to 10% n the Solvent by Weight of the solvent mixture.

Some of the solvents which have been added to cellufoufiwing illustrates, Pe of our invention lose derivative coatings do not provide satisfactory prodbut 15 Intended to hmlt 1t any ucts because of the formation of by-products in the cellusoluuons PriiPared from ce11u1se tr1aetat e lose ester coating or due to the dl-fliculty in removing mg a concentration of 17 g. cellulose triacetate in 100 residual solvents. Others afiect the dimensional stability, of a solvent fixture havmg the followmg Proportlonsi curl resistance, flexibility and the like. We have found Parts by weight certain new solvents which can be used for this purpose Methylene chloride 89 5 which not only do not have a detrimental efiect on the 3 Methyl alcohol cellulose film but improve characteristics such as dimen- Liquid coagulamu 4.6 sional stability in water and the like. u

The advantages of the new coagulants are permitting A series of samples were prepared either containing rapid coating, improving the final products, and obtaining various coagulants according to the invention or prepared more eflicient use of coating equipment. This is particu- 40 using butanol as the known coagulant without a plastilarly important in the case of multiple hopper operations, cizer. A series of samples was also prepared containing such as those where two hoppers or more are used on either one of various coagulants according to our invena single coating wheel. In these coating operations it is tion or with butanol and with triphenyl phosphate as a desirable to have the material gel as soon as possible in plasticizer in an amount of about 15% by weight based order to provide a surface for a succeeding coating. Typion the cellulose acetate. For each series a control samcal multiple hopper coating operations are described in pic was prepared without any coagulant.

United States patent application Ser. No. 721,784, filed The samples were obtained by coating on glass at room M h 17 1958, temperature and dried for minutes at C. after One object of this invention is to provide a process for stripping the sample from the support. rapid coating of cellulose derivative dopes. Another 0b- 50 The results of the tests obtained from the samples withject is to provide coagulants for cellulose derivative dopes out a plasticizer are contained in Table II, while Table II which improve the dimensional stability, flexibility and indicates the results of testing the plasticized samples.

Table I Tensile Eercent Albert Dimenstrength elouga- Schopper Twing slonal Coagulant tnKgJ tion Folds Tearin stability mm? before grams (swell breaking percent) Control without butanol 11. 0 22 21 28 1. 40 Butanol 12. 5 25 25 35 1. 13 2,2,4-trimethyl cyclohexanone 8. 4 28 51 44 0. 52 2,2,5,5-tetramethyl-L3-dioxane 10.5 28 3s 4a 0.66 2-isopropyl-5,5-dimethyl-1,3-dioxane 8. 7 30 50 37 0. 66 2-isopropyl-4,4,6-trimethy1-L3-dioxane 7. 6 2s 54 27 0. 4s

Table 111 Albert Tear in grams Percent elongation before breaking Tensile strength coagulant in KgJmm.

(swell percent) 1,3-dioxane 2-isopropyl-5,5 methyl-1,3-

dioxane 2,2,4-trimethyl-cyclohexanone.

The size of the sample which was used to determine the various tests was in all cases.

The Schopper fold test is the standard A.S.T. test designated D643-43, method A, the Schopper folding endurance test.

The Albert Twing test is the force in grams necessary to tear a piece of film 70 x 150 mm., 55 mils. in thickness after nicking the film.

The dimensional stability to water is a determination widthwise. Two perforations actually inches apart are made in each sample and measurements from outside edge to outside edge of the perforation holes are taken using a gauge graduated in thousandths of an inch. The samples are conditioned at 50% relative humidity for 2 hours, placed in a water bath at 100 F. and left for 17 hours. They are then dried at 50% relative humidity and 68 F. for 48 hours and measured; and then placed in a water bath at 68 F. for 17 hours and measured again. The diifercnces betwen the two measurements is used to give the swell per cent widthwise.

From the above data it can be seen that there is an improvement in the dimensional stability to water of the films prepared with the new coagulating agents of to 25% as compared to the films coated in identical conditions with butanol.

Various coating methods may be used which are within the skill of the art such as hopper coatings, knife coatings, and the like, since the improvement is due to the incorporation of the coagulating agents and not to the type of coating used. Although the coagulation is shown above with cellulose triacetate having about 42.5-44% acetyl content, these coagulants can also be used with other cellulose derivatives, such as cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and the like. a

The proportions of methylene chloride'and of methanol in the solvent mixture given above can be varied between 65 and 90% for methylene chloride and 25 to 5%.

for a lower alcohol such as a methanol.

The coagulants according to our invention such as the metadioxanes can be advantageously utilized alone or mixed with lower alcohols such as methanol and ethanol, as constituents of coagulation baths for the process of fabricating films by coating in a coagulation bath.

We claim:

1. A process for obtaining cellulose triacetate film comprising preparing a film-forming composition with cellulose triacetate and an organic solvent mixture of 65-95% by weight methylene chloride and 25-5% lower alcohol and containing 10% by weight of the solvent mixture of a coagulating agent selected from the class consisting of trimethylcyclohexanone and metadioxane having the following formula:

7 R3\R1 in which R -R are selected from the class consisting of H and saturated hydrocarbon radicals such that the molecular weight of the metadioxane is within the range of 116-230 and coating the film-forming composition on a highly polished coating surface to form a film, removing the film from the casting surface and drying.

2. A film-forming composition for casting films having improved dimensional stability obtained by coating on a highly polished casting surface, consisting essentially of cellulose triacetate having an acetyl content of 42.5- 44% and an organic solvent mixture of 65-95% by weight methylene chloride and 25-5% lower alcohol and containing 5-10% by weight of the solvent mixture of a coagulating agent selected from the class consisting of trimethylcyclohexanone and metadioxane having the following formula:

in which R -R are selected from the class consisting of H and saturated hydrocarbon radicals such that the molecular weight of the metadioxane is within the range of 116-230.

3. A film-forming composition for obtaining films having improved dimensional stability by coating on a highly polished casting surface, consisting essentially of cellulose triacetate having an acetyl content of 42.5-44% and an organic solvent mixture of 65-95% by weight methylene chloride and 25-5% lower alcohol and containing 5-10% by weight of the solvent mixture of 2-isopropyl-5, S-dimethyl-l, 3-dioxane.

References Cited in the file of this patent UNITED STATES PATENTS 2,041,692 Blake et a1. May 26, 1936 2,045,843 Dreyfus June 30, 1936 2,362,307 Ritter Nov. 7, 1944 

2. A FILM-FORMING COMPOSITION FOR CASTING FILMS HAVING IMPROVED DIMENSIONAL STABILITY OBTAINED BY COATING ON A HIGHLY POLISHED CASTING SURFACE, CONSISTING ESSENTIALLY OF CELLULOSE TRIACETATE HAVING AN ACETYL CONTENT OF 42.544% AND AN ORGANIC SOLVENT MIXTURE OF 65-95% BY WEIGHT METHYLENE CHLORIDE AND 25-5% LOWER ALCOHOL AND CONTAINING 5-10% BY WEIGHT OF THE SOLVENT MIXTURE OF A COAGULATING AGENT SELECTED FROM THE CLASS CONSISTING OF TRIMETHYLCYCLOHEXANONE AND METADIOXANE HAVING THE FOLLOWING FORMULA: 